Supercritical noble gases and coloring methods

ABSTRACT

A coloring system can include a noble gas, colorant, and one or more vessels configured to convert the noble gas into a supercritical fluid, and/or receive and color an article of manufacture with the noble gas in the supercritical fluid state. A coloring process can include converting a noble gas into a supercritical fluid state; dissolving, suspending, or absorbing a colorant into the supercritical noble gas, and coloring an article of manufacture with the noble gas in the supercritical fluid state. A coloring composition can include a noble gas in a supercritical fluid state, and a colorant located in the supercritical noble gas.

BACKGROUND

Traditional water-based coloring compositions that are used for dying,staining, or pigmenting an article of manufacture can result in a largevolume of waste water. Often, the waste water can be contaminated withhighly toxic chemicals that are byproducts from the coloring process andthat can be difficult and expensive to separate from the water. However,the contaminated water should not be introduced back into theenvironment without removing the coloring, and as a result an expensivecoloring process may be required.

Supercritical carbon dioxide has been used in coloring processes becauseit can dissolve or absorb the colorant for application to an article ofmanufacture. However, carbon dioxide can also react with variousfunctional moieties on either the colorant or the article ofmanufacture, such as textiles, and impair the ability of the colorant toattach to the article of manufacture. As a result, the colorant islikely to be easily removed from the article, such as during cleaning,so that the color of the article dulls over time.

As such, there is a continued need for improved coloring compositionsthat can be used to provide color to articles of manufacture, such astextiles, polymer parts, metal parts, ceramic parts, or others.

SUMMARY

In one embodiment, a composition can be configured for use as asupercritical noble gas that is capable of coloring an article ofmanufacture. The coloring composition can include a colorant, and anoble gas in a supercritical fluid state having the colorant. Thecomposition can also include an article of manufacture capable of beingcolored with the colorant in the supercritical fluid. The colorant canbe a dye, such as an organic dye or an inorganic dye, as well as apigment or a stain.

In one aspect, the coloring composition can include an additionalsubstance selected from a different noble gas, carbon dioxide, air,oxygen, nitrogen, water, alcohols, aldehydes, amines, hydrocarbons,aromatic hydrocarbons, phenols, bleaches, or combinations thereof.

In one embodiment, a coloring system can be used for coloring an articlewith the coloring composition having the supercritical noble gas andcolorant. The coloring system can include: a noble gas; a colorant thatis miscible in the noble gas in a supercritical state; and one or morevessels configured to (1) convert the noble gas into a supercriticalfluid, or (2) receive and color an article of manufacture with noble gasin the supercritical fluid state having the colorant. The colorant canbe dissolvable, suspendable, or absorbable in the noble gas in thesupercritical state.

In one aspect, the coloring system can have a supercritical fluid vesselconfigured to convert the noble gas to a supercritical fluid. Also, thecoloring system can include a pressure unit configured to increasepressure of the noble gas to or past the supercritical pressure of thenoble gas. Additionally, the coloring system can include a heating unitconfigured to increase temperature of the noble gas to or past thesupercritical temperature of the noble gas. Furthermore, the coloringsystem can have a coloring vessel configured to receive the noble gas ina supercritical fluid state, to receive a colorant, and to receive anarticle of manufacture to be cleaned. Moreover, the coloring system caninclude a separation vessel configured to receive the noble gas with thecolorant or byproduct of the colorant from a coloring vessel and todecompress the noble gas to a gaseous state.

In one aspect, the coloring system can include at least one additionalsubstance to be combined with the noble gas in the supercritical fluidstate. Examples of the additional substance can be selected from adifferent noble gas, carbon dioxide, air, oxygen, nitrogen, water,alcohols, aldehydes, amines, hydrocarbons, aromatic hydrocarbons,phenols, bleaches, or combinations thereof.

In one aspect, the noble gas can be selected from helium, argon,krypton, xenon, neon, radon, or combination thereof.

In one embodiment, the coloring composition and coloring system can beused in a coloring process for coloring an article of manufacture. Thecoloring process can include: converting a noble gas into asupercritical fluid state; combining a colorant with the noble gas inthe supercritical fluid state; and coloring an article of manufacturewith the noble gas in the supercritical fluid state having the coloranttherein.

In one aspect, the coloring process can include comprising combining anadditional substance with the noble gas in the supercritical fluid statebefore or during the coloring. The additional substance can be asdescribed herein.

In one aspect, the coloring process can include: introducing the noblegas in the supercritical fluid state into a coloring vessel; introducingthe colorant into the coloring vessel; introducing the article ofmanufacture into the coloring vessel; and coloring the article ofmanufacture with the noble gas in the supercritical fluid state havingthe colorant therein within the coloring vessel.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a schematic of a prior art and generic phase diagram showing,solid, liquid, gas, and supercritical fluid phases.

FIGS. 2A-2C are schematic diagrams of illustrative embodiments ofcoloring vessels.

FIGS. 2D-2H are schematic diagrams of illustrative embodiments ofcolorant holders that can contain and release the colorant during acoloring process.

FIG. 3 is a schematic diagram of an illustrative embodiment of acoloring system.

FIG. 4 is a schematic diagram of an illustrative embodiment of aseparation vessel.

FIG. 5 is a schematic of an illustrative embodiment of a chemicalreaction between a natural fiber and an isoquinoline derived dye.

FIG. 6 is a schematic of illustrative embodiments of chemical reactionsbetween carbon dioxide and various dyes.

DETAILED DESCRIPTION

In the following detailed description, reference is made to theaccompanying drawings, which form a part hereof. In the drawings,similar symbols typically identify similar components, unless contextdictates otherwise. The illustrative embodiments described in thedetailed description, drawings, and claims are not meant to be limiting.Other embodiments may be utilized, and other changes may be made,without departing from the spirit or scope of the subject matterpresented herein. It will be readily understood that the aspects of thepresent disclosure, as generally described herein, and illustrated inthe figures, can be arranged, substituted, combined, separated, anddesigned in a wide variety of different configurations, all of which areexplicitly contemplated herein.

In view of the problems with coloring process byproducts being toxic orenvironmentally unfriendly, and being costly to prepare for disposal, itwould be beneficial to have a new coloring composition that does nothave these problems. It has now been found that a noble gas in thesupercritical fluid state (e.g., supercritical noble gas) can be used asa non-toxic colorant composition that can dissolve, suspend, or absorb acolorant and apply a colorant to an article of manufacture. The use of asupercritical noble gas coloring composition has minimal to no harmfuleffects on the environment or on human health. Additionally, noble gasescan be easily separated from the coloring process byproducts byconverting the noble gas back to its gaseous state such that thebyproducts from the coloring process remain as solids or liquid. Thegaseous noble gas can then be removed from the liquid and solidbyproducts by venting the gas out of a vessel that retains the liquidand solid. Evaporation of the noble gas may also be useful for removingthe noble gas from the byproducts.

FIG. 1 is a schematic graph that generally represents the solid, liquid,gas, and supercritical fluid states. Noble gases can include helium,argon, krypton, neon, and xenon, or combinations thereof. However, radonmay also be useful in some applications where radioactivity is notproblematic, such as coloring a radioactive material. The noble gasesare substantially inert, non-toxic, and are colorless and tasteless. Thenoble gases can be converted to supercritical fluids by compression to,or past, their supercritical point. The supercritical noble gases areuseful as coloring compositions that provide coloring agents forcoloring purposes, such as coloring various articles of manufacturecomposed of fiber, textile, polymer, glass, ceramic, metal, orcombinations thereof.

A noble gas becomes a supercritical fluid noble gas at a temperature andpressure above its supercritical point. The supercritical point, asshown in FIG. 1, is a well established phenomenon where a gas, such as anoble gas, converts to a supercritical fluid above the temperature(e.g., supercritical temperature) and pressure (e.g., supercriticalpressure) of the supercritical point. As a supercritical fluid noblegas, it can diffuse through solids like a gas, and dissolve materialslike a liquid. In addition, close to the supercritical point, smallchanges in pressure or temperature result in large changes in thedensity of the supercritical fluid, allowing many properties of asupercritical fluid noble gas to be “fine-tuned” to be more liquid likeor more gas like. Relatively small decreases in temperature toward thesupercritical point from temperatures near the supercritical can resultin the supercritical fluid behaving closer to a fluid. Correspondingly,relatively small increases in the temperature away from supercriticalpoint from temperatures near the supercritical can result in thesupercritical fluid behaving closer to a gas. On the other hand,relatively small increases in pressure can increase the density of thesupercritical fluid so that it behaves more like a liquid, whereasrelatively small decreases in pressure reduce the density so that thesupercritical fluid behaves more like a gas. In addition, there is nosurface tension in a supercritical fluid, as there is no liquid/gasphase boundary.

Further, colorants are soluble in the noble gas supercritical fluid.Solubility in a supercritical fluid tends to increase with density ofthe fluid (at constant temperature). Since density increases withpressure, solubility tends to increase with pressure. At constantdensity, solubility will increase with temperature. However, close tothe supercritical point, the density can drop sharply with a slightincrease in temperature. Therefore, close to the supercriticaltemperature, solubility often drops with increasing temperature, andthen rises again. These parameters can be modulated during coloring witha coloring agent suspended in the supercritical fluid to enhancecoloring processes. For example, the solubility of the colorant in thesupercritical fluid can be increased so that more colorant is dissolvedand provided to the article to be colored. However, a dye with lowersolubility in the supercritical fluid can be beneficial in someinstances because it may be easier to control the amount of dye reactingwith the article being colored with a dye with low solubility.

For example, these parameters can be modulated in order to achievecavitation or the formation of bubbles on the surfaces of the vessel aswell as on the article within the vessel. Cavitation can be induced byvarying the pressure (e.g., reduce pressure until boiling occurs), byphysical agitation, by application of ultrasound which induces localizedcavitation upon the surface, and possibly by microwaves. The use ofmicrowaves could greatly enhance and speed the dye-fabric bond formationprocess for some dye fabric combinations. Cavitation can increase thecoloring potential of the solvent. Cavitation would normally nucleate atsurface irregularities upon the item being colored or on the vesselwalls.

All supercritical fluids are miscible with each other so, for a mixture,a single phase can be obtained if the supercritical point of the mixtureis exceeded. The supercritical point of a binary mixture can beestimated as the arithmetic mean of the supercritical temperatures andpressures of the two components:

T _(c(mix))=(mole fraction A)×T _(c) A+(mole fraction B)×T _(c) B.

For greater accuracy, the supercritical point can be calculated usingequations of state, such as the Peng Robinson, or group contributionmethods. Other properties, such as density, can also be calculated usingequations of state. Tertiary, quaternary, or other multiple substancecombinations are also possible. Experimental methods can be useful fordetermining the supercritical point of compositions that have multiplesubstances that are combined for preparing the supercritical fluid.Also, engineering handbooks can be used for looking up values fortertiary systems.

Many pressurized gases are actually supercritical fluids, and therebycan be useful in coloring processes with the supercritical noble gas.For example, nitrogen has a supercritical point of about 126.2K (−147°C.) and about 3.4 MPa (34 bar or 33.56 atmospheres) and carbon dioxide(CO₂) has a supercritical point of about 31° C. and about 75 atmosphere.Therefore, nitrogen or CO₂ in a gas cylinder (e.g., an example of astorage vessel described below) above its respective supercritical pointis a supercritical fluid and may be used in combination with asupercritical noble gas for coloring purposes.

The noble gases are a series of gases that have their valence of s2(helium) or s2p6 (neon, argon, krypton, and xenon) completely filled,and as such are inert to chemical reactions. Argon constitutes about 1%of earth's atmosphere and as such is plentiful. The abundance of kryptonin the atmosphere is thought to be about 0.000108-0.000114%, making itthe seventh most common gas in the atmosphere. Xenon is a trace gas inEarth's atmosphere. Thus, there is a sufficient source of noble gases sothat their use in coloring compositions can be cost effective evenwithout considering the added benefit of improved personal safety andreduced environmental impact.

Supercritical noble gases are capable of dissolving, suspending, and/orabsorbing a wide variety of colorants, such as but not limited to dyes,pigments, stains, or others. The supercritical noble gases have similaror better dissolving and/or absorbing parameters compared with CO₂. Assuch, supercritical noble gases can be used for providing a colorant tocolor articles of manufacture (e.g., textiles) equally as well, if notbetter than, supercritical CO₂. However, the noble gases offer distinctadvantages as they are not carcinogens or mutagens, they do not destroythe ozone layer, they do not behave as green house gases, they arevolatile organic compound (VOC) compliant, and they have no known shortor long term health consequences. Additionally, supercritical CO₂ canreact with articles of manufacture and have a negative impact on thecondition of the article, such as a textile, and lead to degradation ofthe article. Supercritical noble gases are substantially inert and donot have the same potential for reacting with and deteriorating anarticle being colored.

The colorant for coloring the article can be mixable or miscible withthe supercritical noble gas. By being “mixable” or “miscible” it ismeant that the colorant can be dissolvable, suspendable, absorbable, orotherwise capable of being partitioned into the supercritical noble gasthrough any other physical or chemical action or force.

Supercritical fluids of the noble gases, especially argon due to itsabundance and availability to be obtained in a suitable purity, can beused as a carrier for a colorant at supercritical conditions. Argon hasa supercritical temperature and pressure of about −122° C. and about 50atmospheres. Xenon has a supercritical point of about 17° C. and about60 atmospheres. Helium has a supercritical point of about −267.96° C.and about 2.24 atmospheres. Krypton has a supercritical point of about−63.74° C. and about 54.28 atmospheres. Neon has a supercritical pointof about −228.75° C. and about 27.24 atmospheres. For comparison, thecarbon dioxide supercritical pressure is about 75 atmospheres andsupercritical temperature is about 31° C. Therefore, supercriticalapplications using carbon dioxide typically operate at temperaturesbetween about 32 and about 49° C. and pressures between about 75 andabout 250 atmospheres. At temperatures between about 32 and about 49°C., the operational pressure for argon would roughly be between about350-500 atmospheres, which is easily obtainable by modern compressiontechnology. Xenon would roughly be between about 75 and about 250atmospheres.

Under these conditions, an article of manufacture can be colored with acolorant carried by a supercritical noble gas in less than about 30minutes (e.g., about 1 minute to about 30 minutes), less than about 20minutes (e.g., about 5 minutes to about 30 minutes), or even less thanabout 15 minutes (e.g., about 10 minutes to about 15 minutes), whereabout 12 minutes can be an example of a coloring time. Suchsupercritical noble gas can be used to color an article in a mannersimilar to coloring methods performed with supercritical carbon dioxide(CO₂) carrying a colorant under moderate pressure and temperatureconditions that are easily obtainable with industrial heaters,compressors, and pressurizers.

In one embodiment, the colorant can be a dye. A dye is a molecule orchemical which absorbs light more at some visible wavelengths than atothers. When a dye is added to a clear article, it can give clear colorsthat are transparent. In some instances the dye can result in a cleararticle being milky or translucent from the coloring. When a dye isadded to an opaque medium such as concrete, the opacity remains, andsome color is added. The net gray-equivalent brightness is alwaysreduced, because a dye can absorb light.

The dye can be organic or inorganic, synthetic or natural. Organic dyesare well known, and many include reactive groups that can react with anarticle of manufacture, such as textile fibers, for providing a colorfast article with color durability. For example, many dyes have certainreactive moieties, such as amino, carboxyl, or hydroxyl groups that canreact with the article of manufacture to bond therewith. Some examplesof organic dyes are provided below.

3-hydroxy-4′-N,N-dimethylaminoflavone

6-(2-aminoethylamino)-2-isobutyl-1H-benzo[de]isoquinoline-1,3(2H)-dione

(2-hydroxyethyl)(methyl)amino)-2-isopropyl-1H-benzo[de]isoquinoline-1,3(2H)-dione)

1H,1′H-[2,2]Biindolylidene-3,3′-dione

{4-[2-(4-Ethenesulfonyl-phenyl)-vinyl]-phenyl}-diethyl-amine

In one embodiment, the dye is a natural colorant, such as from a plant,animal, or insect product, and possibly from fungi or mushrooms. Somenon-limiting examples of plant dyes can include: catechu (brown) whichis from resin of acacia tree; fustic (yellow) which is from the wood ofthe fustic tree; henna (orange-red) which is from leaves of the hennaplant; indigo (blue) which is from leaves and stems of the indigo plant;logwood (black) which is from the core (heart) of the logwood tree;madder (Turkey red) which is from the roots of the madder plant;quercitron (yellow) which is from the inner bark of the black oak tree;saffron (yellow) which is from stigmas of the common crocus; turmeric(violet) which is from roots of the turmeric plant; as well as others.Non-limiting examples of animal or insect dyes can include: cochineal(red) which is from bodies of cochineal insects; tyrian purple (purpleor crimson) which is from the bodies of some types of marine snails;sepia (brown) which is from secretions of several types of cuttlefish;as well as others.

In one embodiment, the dye is an inorganic dye sometimes referred to asa mineral dye. Mineral dyes come from ocher (yellow, brown, red),limestone or lime (white), manganese (black), cinnabar and lead oxide(red), azurite and lapis lazuli (blue), and malachite (green). Somemineral dyes such as prussian blue, manganese bronze, chrome yellow,antimony orange, or iron buff pigments can be fixed to fibers, such ascotton, by using heat and acid, which can be mixed with thesupercritical noble gas. While some mineral colorants are termed “dyes,”they may actually be pigments. Non-limiting examples of mineral dyes caninclude: chrome green which is from a compound of chromium and oxygen;chrome red which is from a compound of chromium and lead; chrome yellowwhich is from a compound of chromic acid and lead; prussian blue whichis from a compound of iron and cyanide; or others.

In one embodiment, the colorant can be a pigment, which is meant torefer to a mixture or combination of a dye and an opacifying agent, suchas white oxide powders, which scatter light, or dark colored powders,which both absorb and scatter light. Pigments are more opaque, and lookmore like paint. A white or light-colored pigment can sometimes make adark medium lighter, provided the original medium was more translucentthan the pigment. Silver or metallic colorants can be pigments.

In one embodiment, the colorant can be a stain, which tends to be a dyewith selective uptake into an article being colored. For example, whenthe article of manufacture includes a wood product, the colorant can bea stain that stains the wood as the term is traditionally understood.Typically, stained objects get darker by retaining more of the colorant.Wood stains intensify the visibility of the wood's grain. Biologicalstains selectively color certain substances for viewing in themicroscope.

In one embodiment, the article of manufacture to be colored can includea textile article of manufacture. A textile is a flexible materialconsisting of a network of natural, artificial, or synthetic fibersoften referred to as thread or yarn. Yarn is produced by spinning rawwool fibers, linen, cotton, or other material on a spinning wheel toproduce long strands. Textiles are formed by, for example, weaving,knitting, crocheting, knotting, or pressing fibers together (felt). Thewords fabric and cloth are used in textile assembly trades (such astailoring and dressmaking) as synonyms for textile. Textile refers toany material made of interlacing fibers. Fabric refers to any materialmade through weaving, knitting, crocheting, or bonding. Cloth refers toa finished piece of fabric. Examples of textiles that are non-limitingcan include clothing, containers, bags, baskets, carpeting, upholsteredfurnishings, window shades, towels, coverings for tables, beds, andother flat surfaces, filters, flags, backpacks, tents, nets, coloringdevices, handkerchiefs, rags, balloons, kites, sails, parachutes, rope,floor mats, doormats, brushes, mattresses, floor tiles, and sacking, orothers. Textile materials can include animal hairs, wool, silk, grass,rush, hemp, sisal, coconut fiber, straw, bamboo, cotton, flax, jute,hemp, modal and even bamboo fiber, polyester, aramid fibers, acrylicfibers, nylon fibers, spandex, olefin fibers, lurex, or others.

In one embodiment, the article of manufacture can be made of a metal ormetal alloy. Industrial parts or machinery can be colored with thesupercritical noble gas coloring compositions and processes describedherein. Any type of metal or alloy is suitable, such as withoutlimitation, steel, stainless steel, nitinol, aluminum, or others. Metalscan be colored with various pigments and dyes. Also, the metal may needadditional manufacturing or processing to better adhere the colorant tothe metal.

In one embodiment, the article of manufacture can be made of a ceramic.Dishes, pottery, bricks, pipes, floor, roof tiles, porcelain, china orothers can be articles of manufacture prepared from a ceramic. Examplesof ceramic materials that are non-limiting can include alumina oxide,zirconia oxide, carbides, borides, nitrides, silicides, or others.Porous ceramics may be easily colored with the supercritical colorantcomposition. Also, the ceramic may need additional manufacturing orprocessing to better adhere the colorant to the ceramic.

In one embodiment, the article can be glass.

In one embodiment, the article of manufacture can be a polymer orplastic article. The polymer or plastic can be resistant to theconditions of the coloring process, such as temperature and pressure, soas to be stable and not significantly degrade during the coloring.Polyurethanes, polycarbonates, polyacrylamides, polystyrene, polyester,or others are non-limiting examples.

Supercritical noble gas can be combined with one or more hydrocarbonsfor use in the coloring purposes. Mixtures of supercritical noble gaseswith hydrocarbons can be useful in coloring semiconductors. Also, thesupercritical noble gases greatly reduce the amount of hydrocarbonsolvents typically used during coloring processes. For example, argoncan be combined with butane and formed into a supercritical mixture ofabout 1:2 to about 1:3 argon/butane. However, the ratio could range fromabout 10:1 to about 1:1, about 8:1 to about 1:1, or about 5:1 to about1:1, or vice versa. The mixture can be converted to a supercriticalfluid by obtaining a pressure of about 34 MPa (335 atmospheres) andtemperature of about 20° C. The argon/butane can be used to carry acolorant to color the article in a coloring process for a durationrecited herein or less. Other hydrocarbons that can be combined with asupercritical noble gas can include without limitation methane, ethane,propane, butane, ethylene, propylene, or any C1-C20 hydrocarbon that issubstituted or unsubstituted with functional groups, or branched orun-branched, or cyclic or acyclic, or aromatic or aliphatic. In oneaspect, an embodiment of the coloring composition specifically excludesthe use of a hydrocarbon, or one or more specific hydrocarbons, in thenoble gas supercritical fluid coloring composition that isenvironmentally friendly.

The supercritical noble gas can also be combined with one or moreadditional gases in order to prepare the supercritical coloringcomposition. The additional gases can be used to modulate the van derwalls forces, which can change from noble gas to noble gas. As such,induced dipole is larger as the noble gas becomes heavier, and theadditional gases can counteract or amplify these changes. Also, thenoble gas can become softer in character (hard/soft theory) as the gasbecomes heavier, and the additional gases can counteract or amplifythese changes. The additional gases can be used to counteract or amplifythese properties to change the solubility parameters of thesupercritical noble gas fluids and thereby allow for improved ability tosuspend colorant and impart the colorant to the article. Non-limitingexamples of gases that can be used include a different noble gas, carbondioxide, air, oxygen, nitrogen, or others. It can be beneficial for theadditional gas to be non-reactive or have a minimal reactive profile inthe conditions suitable for contacting a particular article with thesupercritical coloring composition. The ratio of noble gas to additionalgas can range from about 10:1 to about 1:1, about 8:1 to about 1:1, orabout 5:1 to about 1:1, or vice versa. The duration of coloring can besimilar to the length of time described herein or even shorter. In oneaspect, an embodiment of the coloring composition specifically excludesthe use of an additional gas in the noble gas supercritical fluidcoloring composition.

The supercritical noble gas can also be combined with water to form acoloring composition. Water is commonly used in many coloringapplications. However, water cannot be mixed with carbon dioxide becausewater reacts with carbon dioxide to form carbonic acid and carbonates.Now water can be combined with the supercritical noble gases so that thecoloring benefits of water can be used in a supercritical fluid. Mixingwater with noble gases can produce supercritical fluids that dissolvehighly ionic colorants while still reducing water waste since it doesnot take much water to give the desired effect. While the use ofsupercritical noble gases can replace the use of water and reduce theenvironmental impact of coloring process, use of some water insupercritical coloring compositions can provide an appreciable benefitof water. The ratio of noble gas to water can range from about 10:1 toabout 1:1, about 8:1 to about 1:1, or about 5:1 to about 1:1, or viceversa. The duration of coloring can be similar to the length of timedescribed herein or even shorter. In one aspect, an embodiment of thecoloring composition specifically excludes the use of water in the noblegas supercritical fluid coloring composition for an environmentallyfriendly coloring composition.

The supercritical noble gas can also be combined with one or morealcohols to prepare a coloring composition. However, alcohols cannot bemixed with carbon dioxide because the alcohols react with carbon dioxideto form organo-carbonates. Now alcohols can be combined with thesupercritical noble gases so that the ability of alcohols to dissolve acolorant can be used in a supercritical fluid. Non-limiting examples ofsuitable alcohols include methanol, ethanol, propanol, n-propanol,isopropanol, or others. The ratio of noble gas to alcohol can range fromabout 10:1 to about 1:1, about 8:1 to about 1:1, or about 5:1 to about1:1, or vice versa. The duration of coloring can be similar to thelength of time described herein or even shorter due to the solventcharacteristics of alcohols. In one aspect, an embodiment of thecoloring composition specifically excludes the use of an alcohol in thenoble gas supercritical fluid coloring composition for anenvironmentally friendly coloring composition.

The supercritical noble gas can also be combined with an organic solventto form a coloring composition where the organic solvent can facilitateuptake of the colorant. Initially, the colorant can be soluble orabsorbable into an organic solvent so that the colorant can more easilypartition into the supercritical fluid upon exposure thereto, which canincrease the ability to color an article of manufacture. Examples oforganic solvents can include but are not limited to acetone, toluene,turpentine, methyl acetate, etheyl acetate, hexane, petrol ether, citrusterpenes, n-pentate, ethylene dichloride, dioxane, dimethyl sulfoxide,acetonitrile, pyridine, acetic acid, THF, methyl isobutyl ketone,methylene chloride, isooctane, cyclohexane, cyclopentane, carbondisulfide, carbon tetrachloride, o-xylene, benzene, dietheylether,chloroform, or others. The ratio of noble gas to solvent can range fromabout 10:1 to about 1:1, about 8:1 to about 1:1, or about 5:1 to about1:1, or vice versa. The duration of coloring can be similar to thelength of time described herein or even shorter due to the solvatingability of the solvent with regard to the colorant. In one aspect, anembodiment of the coloring composition specifically excludes the use ofa solvent in the noble gas supercritical fluid coloring composition tobe more environmentally friendly.

The supercritical noble gas can also be combined with one or more aromacompounds (e.g., fragrances) that can beneficially provide a nice smellto the article being colored, which can be advantageous especially fortextiles. For example without limitation the aroma compound can befragrances, essential oils, perfumes, methyl formate, methyl acetate,methyl butyrate, methyl butanoate, ethyl acetate, ethyl butyrate, ethylbutanoate, isoamyl acetate, pentyl butyrate, pentyl butanoate, pentylpentanoate, octyl acetate, myrcene, geraniol, nerol, citral, lemonal,citronellal, citronellol, linalool, neriolidol, limonene, camphor,terpineol, alpha-ionone, thujone, benzaldehyde, eugenol, cinnamaldehyde,ethyl maltol, vanillin, anisole, anethole, estragole, thymol, or others.However, in some instances it may be desired to provide a noxious odorto the article being colored, such as when marking an item for anundesirable scent to keep animals or people away from the article.Non-limiting examples of aroma compounds that are noxious odorants caninclude trimethylamine, putrescine, diaminobutane, cadaverine, pyridine,indole, skatole, or others. The ratio of noble gas to aroma compound canrange from about 10:1 to about 1:1, about 8:1 to about 1:1, or about 5:1to about 1:1, or vice versa. The duration of coloring can be similar tothe length of time described herein or even shorter. In one aspect, anembodiment of the coloring composition specifically excludes the use ofan aroma compound in the noble gas supercritical fluid coloringcomposition to provide a substantially scentless composition.

The supercritical noble gas can also be combined with pH adjusters, suchas but not limited to various buffer agents to prepare a coloringcomposition with a colorant. Non-limiting examples of pH adjustersinclude weak acids, weak bases, bicarbonates, ammonias, phosphates,monosodium phosphate, disodium phosphate, hydrochloric acid, sodiumcitrate, citric acid, acetic acid, sodium acetate, borax, sodiumhydroxide, 3-{[tris(hydroxymethyl)methyl]amino}propanesulfonic acid,N,N-bis(2-hydroxyethyl)glycine, tris(hydroxymethyl)methylamine,N-tris(hydroxymethyl)methylglycine,4-2-hydroxyethyl-1-piperazineethanesulfonic acid, or others. The ratioof noble gas to pH adjuster can range from about 10:1 to about 1:1,about 8:1 to about 1:1, or about 5:1 to about 1:1, or vice versa. Theduration of colorant can be similar to the length of time describedherein or even shorter. In one aspect, an embodiment of the coloringcomposition specifically excludes the use of a pH adjuster in the noblegas supercritical fluid coloring composition when pH adjustment is notneeded or desired. These pH adjusters can be favorably used because theydo not react with the supercritical noble gases, where the pH adjustersmay be avoided in carbon dioxide systems due to the reactivity withcarbon dioxide.

In one embodiment, the additional substance combined with thesupercritical noble gas can be capable of either being in asupercritical fluid state when the noble gas is in a supercritical fluidstate or the substance is absorbable into the noble gas in thesupercritical state. In some instances, the additional substance canhave a supercritical point that allows the substance to be in asupercritical fluid state along with the noble gas. In other instances,the combination of the noble gas and additional substance(s) can have asupercritical point where the combination is a supercritical fluid abovethe supercritical point (e.g., above the supercritical temperature andsupercritical pressure for the composition). In other instances, theadditional substance can be dissolved or solvated by or into thesupercritical noble gas. Also, the additional substance can be absorbedor suspended in the supercritical noble gas. For example, a pigmentcolorant can be suspended in the supercritical noble gas. In any event,the supercritical noble gas can form a composition with the additionalsubstance(s) located therein such that the combination of thesupercritical noble gas and additional substance can function in acoloring process to color an article of manufacture. These additionalingredients allow the coloring composition to be tailored for aparticular coloring purpose.

In one embodiment, the additional substance can have a supercriticalpressure that is lower than the supercritical pressure of the noble gas,and/or the additional substance can have a supercritical temperaturethat is lower than the supercritical temperature of the noble gas. Also,the additional substance can have a supercritical pressure that ishigher than the supercritical pressure of the noble gas, and/or theadditional substance can have a supercritical temperature that is higherthan the supercritical temperature of the noble gas. In another example,the supercritical noble gas and additional substance can be prepared asa supercritical fluid at a temperature range from about −50° C. to about50° C., or from about −150° C. to about 150° C., or from about −273° C.to about 500° C. and/or at a pressure range from about 50 atm to about400 atm, or from about 300 atm to about 600 atm, or from about 1 atm toabout 2000 atm. Also, the supercritical point of a composition of noblegas and an additional substance can be obtained through routineexperimentation, and the supercritical point can depend on the nature ofthe additional substance. Accordingly, the supercritical noble gas andadditional substance can be at a temperature and pressure above thesupercritical pressure and/or supercritical temperature of the mixture.

The present disclosure is not to be limited in terms of the particularembodiments described in this application, which are intended asillustrations of various aspects. Many modifications and variations canbe made without departing from its spirit and scope, as will be apparentto those skilled in the art. Functionally equivalent methods andapparatuses within the scope of the disclosure, in addition to thoseenumerated herein, will be apparent to those skilled in the art from theforegoing descriptions. Such modifications and variations are intendedto fall within the scope of the appended claims. The present disclosureis to be limited only by the terms of the appended claims, along withthe full scope of equivalents to which such claims are entitled. It isto be understood that this disclosure is not limited to particularmethods, reagents, compounds compositions or biological systems, whichcan, of course, vary. It is also to be understood that the terminologyused herein is for the purpose of describing particular embodimentsonly, and is not intended to be limiting.

In one embodiment, a coloring system can include a noble gas compositionthat can be converted to a supercritical fluid. Also, the coloringsystem can include a colorant, such as any colorant described herein orothers in the art. A “colorant” can be any type of chemical or substancethat can impart “color” to an article when applied thereto. Commonexamples of colorants are dyes, pigments, and stains. A coloring system,as shown in FIGS. 2A-4 can also include one or more vessels that areconfigured to convert the noble gas into a supercritical fluid and/orreceive and color an article of manufacture with a colorant, dissolved,suspended, or absorbed into the noble gas in the supercritical fluidstate.

FIGS. 2A-2C shows illustrative embodiments of coloring vessels 202 thatcan be configured to color an article (not shown). In FIGS. 2A-2C,features are shown as schematic representations in order to identify thepresence of a feature, while the shape, size, or operationalconfiguration of the feature may differ from that which is actuallyshown. One of skill in the art will recognize that the schematicrepresentations illustrate that a feature may be present, but that thefeature may different in appearance from the example shown in thefigures. The coloring vessel 202 can be configured as any chemicalreaction vessel that is capable of operating at the high temperaturesand pressures and having means (e.g., ports, doors, inlets or the like)for receiving/removing the article of manufacture as well as thesupercritical fluids. The coloring vessel can include any type of shapeof standard chemical reactors, such as spherical, cylindrical, cubic, orother. The coloring vessel 202 can be made of inert metals such asstainless steel and titanium, as well as others.

The coloring vessel 202 may also include a computing system and/orcontroller (not shown) that can receive instructions and operate thecoloring vessel 202 as well as the doors or valves associated therewith.The computing system and/or controller can be configured as is wellknown in chemical processing systems and can communicate with othercomputing systems and/or controllers of other components in the coloringsystem. As such, the computing system and/or controller can becommunicatively coupled with a communication network.

The coloring vessel 202 can include features found on common reactionvessels that are found in laboratory and/or industrial settings. Assuch, the coloring vessel 202 can include one or more inlets with doorsor valves that can selectively open or close the inlet to allow anarticle or supercritical gas to enter into the coloring vessel 202 orclose and stop any additional material from entering into the coloringvessel 202. For example, a door inlet can be useful for moving anarticle into or out from the coloring vessel 202 while a valve inlet canbe useful for receiving the supercritical fluid or removing thecontaminated supercritical fluid from the coloring vessel 202.

The coloring vessel 202 is associated with a noble gas source 204configured to provide the noble gas to the coloring vessel 202 in aliquid, gas, or supercritical state, as well as in a coloringcomposition that optionally includes one or more additional substancescombined with the noble gas. The noble gas source 204 is a schematicrepresentation of an inlet, port, or the like that can supply the noblegas into the coloring vessel 202. The noble gas source 204 is shown as atube that can supply the noble gas to the coloring vessel 202, and itmay include valves, controllers, or other features for supplying thenoble gas into the coloring vessel. The noble gas source 204 is shownsubstantially as a tube that can be connected to a processing component,such as a supercritical vessel that converts the noble gas into asupercritical fluid, that provides the noble gas to the coloring vessel202. Since the noble gas is provided into the coloring vessel 202 as afluid, the noble gas source 204 can have any suitable configuration forsupplying such a fluid.

The coloring vessel 202 is also associated with an article source 206configured for providing the article to be colored into the coloringvessel 202. The article source 206 is a schematic representation of aninlet, port, door, or the like that can supply the article (e.g., one ormore objects) into the coloring vessel 202. The article source 206 isshown as a tube that can supply the article to the coloring vessel 202,and it may include valves, controllers, or other features for supplyingthe article into the coloring vessel. The article source 206 is shownsubstantially as a tube that can be connected to a supply of thearticle; however, the actual appearance of the article source 206 may bedifferent from the illustration. The article source 206 can includeconveyers to carry the article, augers for moving the article when in aparticulate form (e.g., plastic pellets), or mechanical components forobtaining the article and supplying the article into the coloring vessel202.

The coloring vessel 202 can also be associated with a noble gas outlet208 configured to allow the noble gas and coloring byproducts to beremoved from the coloring vessel 202 and separated from the coloredarticle. The coloring byproducts can be dissolved, suspended, orotherwise absorbed into the supercritical fluid so that they can beremoved from the coloring vessel 202 in any manner sufficient for fluidremoval. The noble gas outlet 208 may be configured similarly as thenoble gas inlet 204; however, the direction of flow is out from thecoloring vessel 202. Accordingly, the noble gas outlet 208 is aschematic representation of an outlet, port, or the like that can removethe noble gas and byproducts from the coloring vessel 202. The noble gasoutlet 208 is shown as a tube that can remove the noble gas andbyproducts from the coloring vessel 202, and may include valves,controllers, or other features for removing the noble gas and byproductsfrom the coloring vessel 202. The noble gas outlet 208 is shownsubstantially as a tube that can be connected to a later processingcomponent, such as a vessel that converts the noble gas from beingsupercritical into being a gas state. Since the noble gas is removedfrom the coloring vessel 202 as a fluid, the noble gas outlet 208 canhave any suitable configuration for supplying such a fluid.

Additionally, the coloring vessel 202 can be associated with an articleoutlet 210 configured to allow the removal of the article from thecoloring vessel 202, and which can be configured similarly to thearticle source 206. The article outlet 210 can be configured similarlyas the article source 206. The article outlet 210 is a schematicrepresentation of an inlet, port, door, or the like that can be used toremove the article (e.g., one or more objects) from the coloring vessel202. The article outlet 210 is shown as a tube that can move the articlefrom the coloring vessel 202 and supply the article to storage or forfurther processing, and it may include valves, controllers, or otherfeatures for removing the article from the coloring vessel. The articleoutlet 210 is shown substantially as a tube; however, the actualappearance of the article outlet 210 may be different from theillustration. The article outlet 210 can include conveyers to carry thearticle, augers for moving the article when in a particulate form (e.g.,plastic pellets), or mechanical components that can physically move thearticle.

Optionally, the article source 206 and article outlet 210 can be thesame component. Also, the noble gas source 204 can be the same componentas the noble gas outlet 208.

The coloring vessel in 202 is shown to be devoid of any mechanicalagitating components and the coloring can be performed by thesupercritical noble gas providing the colorant that can color thearticle by being passed over, around, through, or in contact with thearticle. The status of the noble gas as a supercritical fluid can absorbthe colorant into the supercritical fluid so that the colorant is ableto come into contact with the article. The noble gas source 204 andnoble gas outlet 210 may be in continuous operation so that new noblegas is continually introduced into the coloring vessel 202 andcontaminated noble gas with byproducts is continually removed from thecoloring vessel 202, which can cause a supercritical fluid current orflow that moves through the coloring vessel 202 to provide the colorantto the article. Also, the coloring vessel 202 can be outfitted withnozzles (FIG. 2C), blowers (not shown), or other fluidic components thatcan induce the supercritical fluid to flow within the coloring vessel202. Also, the supercritical fluid can have a circulatory environmentwithin the coloring vessel 202, such as by convection, that circulatesthe colorant over, around, or through the article. Also, pressurecycling, which is described in more detail below, within the coloringvessel 202 can facilitate the coloring. For example, the pressurecycling can enhance the dissolving, suspending, or absorption of thecolorant into the supercritical noble gas.

Additionally, the coloring system 200 can include one or more colorantholder 211 that is configured to hold the colorant and provide thecolorant to the supercritical noble gas. The colorant holder 211 can bea permeable container that has at least one surface that is permeable toboth the supercritical noble gas as well as the colorant particles. Thecolorant is optionally provided as a powder, pressed cube, or liquidwithin the colorant holder 211 such that the colorant can be dissolved,suspended, or absorbed into the supercritical noble gas.

FIGS. 2D-2H show representative examples of different colorant holders211 a, 211 b, 211 c, and 211 d. The colorant holder 211 a is configuredas a filter disk with a pore size that is selected to allow colorantparticles smaller than a predetermined size to be passed through thefilter pores. The colorant holder 211 a can include a filter that isconfigured similar to a mesh particle size separator. The colorantholder 211 a can include pore sizes ranging from about 0.5 nm to about500 microns, about 1 nm to about 250 microns, about 25 nm to about 100microns, about 50 nm to about 50 microns, about 100 nm to about 1micron, or about 250 to about 750 nm. The colorant holders 211 b, 211 c,and 211 d, can be similarly configured, but can have: different shapes,different pore sizes, or other configurations.

The holder 211 a of FIG. 2D is shown as in a disk shape that has onlyone surface (cross-hatched) for releasing the colorant. As such, thesize of the surface as well as the mesh size can be modulated fordifferent types of colorants, different colorant release rates, or otherrelease parameters.

The holder 211 b of FIG. 2E is shown to be rectangular with a beveledsurface (cross-hatched) with a smaller cross-sectional area forreleasing the colorant. This shows that the mesh surface can have adifferent size for controlling the release rate of the colorant.

The holder 211 c of FIG. 2F has a cubic shape showing one surface(cross-hatch) active in releasing the colorant. While not shown, theback surface opposite of the cross-hatch surface can also be mesh forreleasing the colorant.

The holder 211 d of FIG. 2G has a cross shape with the entirety of theexternal surface area being mesh (cross-hatch) so as to be capable ofreleasing the colorant from any surface. While not shown, each surfacemay be associated with a particular colorant so that the same holder 211d can retain and release multiple colorants, such as one colorant andcolorant reservoir per surface or per arm of the cross.

The holder 211 e of FIG. 2H has a washer shape with an aperture. Thisconfiguration can allow for the supercritical fluid to pass through theaperture of the washer so that the colorant can be dispersed from theaperture as well as from the outer surfaces.

In one embodiment, the holder 211 can be associated with a controllerand components that can selectively release the colorant as desired,programmed or controlled.

As such, the holder 211 can include a mechanism that can be opened torelease colorant or closed to stop colorant from being released. Thiscan be beneficial with a colorimeter that measures the value of thecolor of the article so that more colorant is added when needed andstopped when the article is sufficiently colored.

In one embodiment, the holder 211 can be configured to retain more thanone type of colorant so that the colorants can be released together orseparately. As such, the holder having more than one color reservoir andbeing associated with a controller can be controlled to release thecolorants together or separately.

FIG. 2B shows a coloring vessel 202 with a mechanical agitator 212;however, multiple agitators 212 can be used. Mechanical agitators 212are well known components of chemical processing and can use any of avariety of agitating members to agitate the supercritical fluid as wellas the article. The mechanical agitator 212 can be configured similarlyas any stirring, mixing, or kneading device, which are well known. Forexample, the mechanical agitator 212 can be a magnetic stirrer. Also,the mechanical agitator 212 may be associated with a controller suchthat it is controllable or programmable, where the controller may becommunicatively coupled with a central computing system or controller.The mechanical agitator 212 can agitate the colorant holder 211, or thecolorant holder 211 can be attached to the interior or the coloringvessel 202 so that it is not impacted by the mechanical agitator.

FIG. 2C shows a coloring vessel 202 with two nozzles 214 configured todirect the supercritical noble gas over the article; however, one ormultiple nozzles can be used. The nozzles can be used to increase therate at which dye is absorbed by the article. The nozzles could be partof a loop where supercritical noble gas fluid is constantly flowed overthe dye to increase the rate of uptake. Furthermore the increased flowrate allows high penetration of the article that dye is being appliedto. The nozzles 214 can be located at any suitable position within thecoloring vessel 202 so that the nozzles 214 blow the supercritical fluidover the holder 211 and/or the article. The nozzles 202 can be fluidlycoupled with the noble gas source 204 so that fresh supercritical fluidis blown, or the nozzles can be coupled with a pump to recyclesupercritical fluid with or without the colorant and blow thesupercritical fluid with or without the colorant.

Additionally, FIG. 2C shows that the coloring vessel 202 can beoutfitted with temperature controlling components 216 configured toallow the coloring vessel to modulate the temperature of the noble gasto above and/or below the supercritical temperature. The temperaturecontrolling components 216 can include without limitation heaters, heattransfer components, heat exchangers, heating jackets, coolers,refrigeration components, cooling jackets, or other temperaturecontrolling components 216. Also, FIG. 2C shows that the coloring vessel202 can be outfitted with pressure controlling components 218 configuredto modulate the pressure above and/or below the supercritical pressure.The pressure controlling components 218 can include without limitationpumps, pressurizers, bleed valves, compressors, or others. Temperaturecontrolling components 216 and pressure controlling components 218 arewell known in the art. Thus, the coloring vessel 202 can receive thesupercritical noble gas and/or convert the noble gas to a supercriticalfluid, and back again to a gas or liquid noble gas.

Additionally, the coloring vessel 202 of FIG. 2C can include nozzles 214that are configured to direct flow of the supercritical noble gas ontoor at the colorant holder 211. The nozzles 214 can blow freshsupercritical noble gas, or the coloring vessel 202 can include pumps orsprayers that can blow supercritical gas from within the coloring vesselout from the nozzles 214.

In one embodiment, the coloring vessel 202 of FIG. 2C can be configuredas a pressure autoclave. Also, the temperature controlling components216 can include an oil heater, heating oil, and an oil jacket that is incontact or around at least a portion of the coloring vessel 202.

FIG. 3 shows another example of a coloring system 300 for use withsupercritical noble gases. Similar to FIG. 2A, the coloring system 300can include a coloring vessel 302 associated with a noble gas inlet 304,an article inlet 306, a noble gas outlet 308, and an article outlet 310,where one or more of these components can be combined. The noble gasinlet 304 can receive the noble gas from a supercritical fluid vessel312 configured to convert the noble gas to a supercritical fluid, suchas by modulating the temperature and/or pressure.

In some instances, the functionality of the supercritical fluid vessel312 can be accomplished with a pressure unit 314 and/or a temperatureunit 316. As such, the pressure unit 314 and/or temperature unit 316 canbe fluidly coupled with the noble gas inlet 304, and further can befluidly coupled with each other so that both temperature and pressurecan be modulated to convert the noble gas to a supercritical fluid. Thepressure unit 314 can be configured to increase pressure of the noblegas to or past the supercritical pressure of the noble gas. Thetemperature unit 316 can include heating components and function as aheater to heat the noble gas above the supercritical temperature. Also,the temperature unit 316 can include cooling components in the instancethat the supercritical noble gas should need to be cooled beforecoloring a particular article. The supercritical fluid vessel 312,pressure unit 314, and/or temperature unit 316 can provide thesupercritical noble gas to the a coloring vessel 302, which isconfigured to receive the noble gas in a supercritical fluid state andto receive an article of manufacture to be colored.

FIG. 3 also shows that the coloring system 300 can be capable ofrecycling the noble gas for use in subsequent coloring processes. Asshown, the coloring vessel 302 is coupled to a separation vessel 318configured to receive the noble gas with one or more coloring byproductsfrom a coloring vessel 302 and to decompress the noble gas to a gaseousstate so that the noble gas can be separated from the one or morecoloring byproducts. Once the noble gas and coloring byproducts areseparated, the noble gas can be recycled by being passed out of theseparation vessel 318 through a recycling outlet 320. The coloringbyproducts that are solid or liquid can be removed from the separationvessel through a colorant byproduct outlet 322 (e.g., waste outlet).

After being removed from the separation vessel 318, the recycled noblegas can be passed into a cooling unit 328 configured to receive thenoble gas in a supercritical fluid state or gaseous state and to reducethe temperature of the noble gas to a liquid state. The cooling unit 328can be outfitted with various cooling components such as refrigerationcomponents and fluids that can cool the noble gas to a liquid.

In one option, the coloring system 300 can include a noble gas storagevessel 324 configured to store the noble gas in a supercritical fluid,gaseous, or liquid state.

The coloring system 300 can also include a fresh noble gas inlet 326 toreceive fresh noble gas into the system. Also, the inlet 326 can receiveother additional substances as described herein. Alternatively, any ofthe components of the system can include an inlet for receiving a noblegas or additional substance.

The coloring system 300 can include one or more fluid passageways 330that connect the components of the coloring system 300 together so thatthe noble gas can flow between the different components while in theliquid, gas, or supercritical state. Also, the dashed box around thecoloring system 300 is meant to illustrate that any of the componentscan be fluidly coupled together with a fluid passageway even if notexplicitly shown. For example, the recycling outlet 320 can be directlyfluidly coupled with the noble gas storage vessel 324, pressure unit314, temperature unit 316, supercritical fluid vessel 312, coloringvessel 302, or others.

The coloring system 300 can also include one or more valves 332 locatedat various positions in the system 300 with respect to the differentcomponents and fluid passageways 330, such as component inlets andoutlets. The valves 323 can regulate the entry or exit of the noble gasto and from the various components, and any component can be outfittedwith one or more valves so that fluid flow can be regulated. The dashedbox around the coloring system 300 is also meant to illustrate that anyof the components can include one or more valves 332 to regulate fluidflow or even the removal of the colorant byproducts from the separationvessel 318. Additionally, the valves 323 can be associated with acontroller that can control the valves 323 to be open or closed as wellas what percentage open the valve is when variable. The controller canallow for the operation of the valves to be controlled or programmed asnecessary or desired. Also, the dashed box can represent that thecontrollers of the valves 323 are in communication with a centralcomputing system or controller, and may be operably coupled with acommunication network.

The coloring system 300 can also include one or more pumps 334 locatedat various positions in the system 300 with respect to the differentcomponents and fluid passageways 330. The pumps 334 can pump the noblegas to and from the various components through the passageways 330. Thedashed box around the coloring system 300 is also meant to illustratethat any of the components can include one or more pumps 334 to regulatefluid flow or even the removal of the colorant byproducts from theseparation vessel 318.

In one embodiment, the coloring system 300 can exclude variouscomponents or the functionality of multiple components can be combinedinto a single component. In instances that the coloring system 300includes a supercritical fluid vessel 312, the pressure unit 314 and/ortemperature unit 316 can be omitted, or vice versa. Also, the storagevessel 324 and cooling unit 328 can be omitted.

In one embodiment, the coloring system 300 can be configured so that thenoble gas having contaminant is obtained and removed from the system,and is not recycled in the system. As such, the separation vessel 318,cooling vessel 328, and storage vessel 324 may be omitted. Also, thevarious fluid passageways 330 may be omitted as the fluids can betransferred between the components manually or by using containers tomove the noble gas around the system 300.

The one or more vessels of the coloring system 300 can be linkedtogether so that the noble gas in the liquid, gas, or supercriticalstate can pass through fluid passageway between the different vessels.Also, the different vessels or components can be configured for aparticular purpose.

A supercritical fluid vessel 312 can be configured to convert the noblegas to a supercritical fluid. As such, the supercritical fluid vessel312 can be outfitted with compressors, pressurizers, coolers, andheaters that are able to increase the pressure and temperature to orpast the supercritical point. The supercritical fluid vessel 312 can becontrolled by a controller (not shown) so that the operation there ofcan be controlled and/or monitored. Also, the supercritical fluid vessel312 can be configured to receive the colorant, with or without acolorant holder, so that the preparation of the supercritical noble gasalso entrains the colorant particles within the supercritical noble gas.

A pressure unit 314 can be configured to increase pressure of the noblegas to or past the supercritical pressure of the noble gas. The pressureunit 314 can be outfitted with compressors, plunger systems, or otherpressurizing components that can increase the pressure of the noble gasto or past the supercritical pressure. The pressure unit 314 can becontrolled by a controller (not shown) so that the operation thereof canbe controlled and/or monitored.

A temperature unit 316 (e.g., heating unit) can be configured toincrease temperature of the noble gas to or past the supercriticaltemperature of the noble gas. The temperature unit 316 can be outfittedwith heating elements, heating fluids, fluid cycling components, heatexchangers, or other components that can be used to increase thetemperature of the noble gas to or past the supercritical temperature.The temperature unit 316 can be controlled by a controller (not shown)so that the operation thereof can be controlled and/or monitored.

A coloring vessel 302 can be configured to receive the noble gas in asupercritical fluid state and to receive an article of manufacture to becolored. Alternatively, the coloring vessel 302 can include componentssimilar to the supercritical unit 312, pressure unit 314, andtemperature unit 316 so that the supercritical state can be achieved,maintain, or modulated in and out of the supercritical fluid state. Thecoloring vessel 302 can be configured similarly to any commonsupercritical chemical reactor or separator. An example of a coloringvessel can be a HPR-Series High Pressure Chemical Reactor fromSupercritical Fluid Technologies. An example coloring vessel 302 can becharacterized as follows: stirred reactor vessel from 50 ml to 800 litercapacity; operate up to 10,000 psi (689 Bar/68.9 MPa/680 atmospheres)and 350° C.; magnetic drive mixing; safety rupture disc assembly;integrated controller with color touch screen; data export via a flashdrive communications port; and/or data export via wire, optical, orwireless communication with a data network. The coloring vessel 302 canbe controlled by a controller (not shown) so that the operation thereofcan be controlled and/or monitored.

A separation vessel 318 can be configured to receive the noble gas withone or more coloring byproducts from a coloring vessel 302. Optionally,the separation vessel 318 can decompress the noble gas to a gaseousstate so that the noble gas can be separated from the solid and liquidcoloring byproducts. Also, the separation vessel 318 can be operatedsimilar to a distillation column or a chromatography column in theability to separate the noble gas from the coloring byproducts. Theseparation vessel 318 can be controlled by a controller (not shown) sothat the operation thereof can be controlled and/or monitored.

A noble gas storage vessel 324 can be configured to store the noble gasin a supercritical fluid, gaseous, or liquid state. Any type of storagevessel with adequate strength can be used depending on the state of thenoble gas. Common chemical tanks may be appropriate.

A cooling unit 328 can be configured to receive the noble gas in asupercritical fluid state or gaseous state and to reduce the temperatureof the noble gas to a liquid state. As such, the cooling unit 328 can beoutfitted with cooling components, refrigeration components,refrigeration fluids, cryogenic components, or others. The cooling unit328 can be controlled by a controller (not shown) so that the operationthereof can be controlled and/or monitored.

The valves 332, pumps 334, or any other components can be controlled bya controller (not shown) so that the operation there of can becontrolled and/or monitored.

In one embodiment, the coloring system 300 can include a mastercontroller (not shown) that is configured to control and/or monitor theoperating conditions and parameters of each of the coloring systemcomponents. The master controller can include a microcontroller toperform all computational, instructional, or data processing functions.The microcontroller and power control components can be located in anymodule which may reside in association of the coloring system 300. Themaster controller can communicate with any of the controllers associatedwith any of the coloring system 300 components. Also, the mastercontroller can be configured similar to a standard computer and includegraphical user interfaces (e.g., computer screen or printer), and inputinterfaces (e.g., keyboard, mouse, light pen, voice recognition, touchscreens, pushbuttons, knobs, etc.). The master controller can implement:temperature control, agitator speed control, pressure control,over-temperature limit control, valve control, pump control, or othercontrolling or monitoring functions. The dashed line box around thecoloring system 300 also illustrates that the master controller cancommunicate with any of the components.

FIG. 4 shows an embodiment of a separation vessel 418. The separationvessel 418 can receive the noble gas and coloring byproducts from thecoloring vessel 302 as shown in FIG. 3. Also, the separation vessel 418can have an inlet 440 that is regulated with a valve 442. The separationvessel 418 can include the recycling outlet 420 that is associated witha valve 442 and coloring byproduct outlet 422. The valve 442 associatedwith the recycling outlet 420 can function as a decompressor so as todecompress the noble gas to a gaseous state. Also shown are atemperature modulating component 424 (e.g., heater or cooler) andpressure modulating component 426 that can operate to modulate thetemperature and pressure in order to facilitate separation of the noblegas from the contaminates. The separation vessel 418 can also include acoloring byproduct outlet 422 that is associated with a valve 442 forremoval of the byproducts from the separation vessel 418. The recyclingoutlet 420 can be configured as a gas outlet that can release the noblegas in the gaseous state from the separation vessel 418.

The coloring systems described herein of course can include the noblegas for use in coloring, whether in the liquid, gas, or supercriticalstate. Also, the coloring system can include at least one additionalsubstance to be combined with the noble gas in the supercritical fluidstate for coloring. The additional substance may be, without limitation,a gas, an alcohol, a hydrocarbon, a halogenated hydrocarbon, a ketone,an aldehyde, an aromatic hydrocarbon, or a phenol, or a combinationthereof. Non-limiting examples of gas can include a different noble gas,carbon dioxide, air, oxygen, nitrogen, water. Non-limiting examples ofhydrocarbon may include methane, ethane, propane, butane, ethylene, andpropylene. Non-limiting examples of alcohol may include methanol,ethanol, n-propyl alcohol, isopropyl alcohol, isobutyl alcohol, andcyclohexanol. Non-limiting examples of ketones may include acetone orcyclohexanone. Non-limiting examples of aldehyde may includeformaldehyde or acetaldehyde. Non-limiting aromatic hydrocarbon mayinclude benezene, toluene, or various isomers of xylenes. Non-limitingexamples of xylenol may include phenol, or various isomers of xylenols.In one aspect, the additional substance is capable of either being in asupercritical fluid state when the noble gas is in a supercritical fluidstate or the substance is absorbable into the noble gas in thesupercritical state.

One skilled in the art will appreciate that, for this and otherprocesses and methods disclosed herein, the functions performed in theprocesses and methods may be implemented in differing order.Furthermore, the outlined steps and operations are only provided asexamples, and some of the steps and operations may be optional, combinedinto fewer steps and operations, or expanded into additional steps andoperations without detracting from the essence of the disclosedembodiments.

The coloring systems shown in FIGS. 2-4 can be used in a coloringprocess for coloring an article of manufacture with the supercriticalfluid. The coloring process described herein can be performed similarlyto coloring processes that have used carbon dioxide in its supercriticalstate. Improvements thereover can include the use of supercritical noblegases that are less reactive and have fewer propensities to damage thearticle being colored. Other advantages of using noble gases aredescribed herein.

In one embodiment, a coloring process can include converting a noble gasinto a supercritical fluid state, and coloring an article of manufacturewith a colorant dissolved, suspended, or absorbed into the noble gas inthe supercritical fluid state so as to color the article of manufacture.The coloring process can be conducted similar to supercritical carbondioxide coloring processes. The noble gas can be a major or minorcomponent in the coloring composition and can range by weight from atleast about 10%, at least about 20%, at least about 30%, at least about40%, at least about 50%, at least about 60%, at least about 70%, atleast about 80%, at least about 90%, at least about 99%, or about 100%by weight. The noble gas can range from about 10% to about 99%, or fromabout 20% to about 80%, or from about 30% to about 70%, or from about40% to about 60%, or about 50% by weight or by volume.

In one embodiment, the coloring process can include combining one ormore additional substances with the noble gas in the supercritical fluidstate before or during the coloring. The mixture can include theadditional substances at various ratios with regard to the noble gas asrecited herein in weight/weight ratios. Some non-limiting examples ofthe additional substance can include a different noble gas, carbondioxide, air, oxygen, nitrogen, ammonia, water, alcohols, methane,ethane, propane, butane, ethylene, propylene, methanol, ethanol,acetone, or combinations thereof as well as others recited herein.

In one embodiment, the coloring process can include cycling the pressureof the noble gas in the supercritical fluid state during the coloring.Such pressure cycling can be done by compression and/or expansion of thecoloring vessel volume, or modulating the pressure by releasing somenoble gas in to or out of the separation vessel. The pressure cyclingcan reduce the pressure of the noble gas below the supercriticalpressure and/or increase the pressure of the noble gas above thesupercritical pressure. For example, the pressure cycling can change thestate of the noble gas from a supercritical fluid to a state where atleast a part of the noble gas is not in supercritical fluid state. Suchpressure cycling can cause nucleation and generation of gas bubbleswithin the supercritical fluid, and some nucleation can occur by thecolorant particles being nucleating agents. Also, the bubble generationcan function similarly as boiling for removing the colorant particlesfrom the colorant holder from the article. Thereby, the nucleation eventcan facilitate coloring the article of manufacture.

In one embodiment, the coloring process can include cycling thetemperature of the noble gas in the supercritical fluid state during thecoloring. The temperature cycling can reduce the temperature of thenoble gas below the supercritical temperature and/or increases thetemperature of the noble gas above the supercritical temperature. Thetemperature cycling can change the state of the noble gas from asupercritical fluid to a state where at least a part of the noble gas isnot in supercritical fluid state. The temperature cycling can alsofacilitate bubble generation.

In one embodiment, the coloring process can include generating bubblesin the presence of the article of manufacture while being colored orintroducing bubbles into the coloring vessel.

In one embodiment, the coloring process can include agitating thearticle of manufacture in a manner that is similar to various coloringmethods that agitate an article to be colored in the presence of acoloring composition. The agitating can be from mechanical agitationwith a stirring mechanism, spinning mechanism, or other agitationmechanism. Also, the agitating can be obtained by bubble generation.

The coloring process can also include removing the noble gas and one ormore byproducts from the article of manufacture. The noble gas andcoloring process byproducts can be removed in a continual basis where afeed of noble gas containing the byproducts is siphoned from thecoloring vessel during the coloring process, and whereby noble gas isoptionally introduced into the coloring vessel to maintain thesupercritical fluid. For example, the siphoning of the noble gas canfacilitate the pressure cycling. Alternatively, the coloring process canoperate on a batch basis where the supercritical noble gas andbyproducts are removed after coloring. In another alternative, the samearticle can undergo multiple cycles of coloring with fresh noble gas andcolorant, which is removed, and then replaced during each cycle.

In one embodiment, the coloring process can include separating the noblegas from one or more byproducts after being removed from the coloringvessel. For example, the separation can be performed in the separationvessel. The separation can include converting the noble gas to a gaseousstate to facilitate separating the noble gas from the one or morebyproducts, which one or more contaminants are in a solid or liquidstate.

In one embodiment, the coloring process can include recycling the noblegas for additional coloring cycles of the same or different articles.The recycling process can include cooling the noble gas from a gaseousstate to a liquid state after being separated from the one or morebyproducts. The liquid noble gas can then be stored in a storage vesselbefore being used again or converted to a supercritical fluid.

In one embodiment, the coloring process can include converting the noblegas to a supercritical fluid after being separated from the one or morebyproducts. As such, the recycling process can include converting thenoble gas to a supercritical fluid before being used again in anothercoloring process.

In one embodiment, the recycling process can include separating thenoble gas from the additional substance after the coloring. Such aseparation can be performed in the separation vessel described herein,or a dedicated separation vessel can be provided in the coloring systemfor separating the noble gas from the additional substances used forcoloring. The separation can be similar to the process for generatingnoble gases from the environment.

In one embodiment, the coloring process can include introducing thenoble gas in the supercritical fluid state into a coloring vessel;introducing the article of manufacture into the coloring vessel;introducing a colorant into the coloring vessel; and coloring thearticle of manufacture with the colorant entrained in noble gas in thesupercritical fluid state within the coloring vessel. Accordingly, thenoble gas can be converted into a supercritical fluid before beingintroduced into the coloring vessel, with or without the colorant.Alternatively, the noble gas can be converted to a supercritical fluidwithin the coloring vessel where the colorant is within the coloringvessel for entrainment within the supercritical noble gas. The articleusually will be introduced into the coloring vessel along with thecolorant, with or without a colorant holder, before the noble gas.

In one embodiment, the coloring process can include increasing thepressure of the noble gas to or past the supercritical pressure of thenoble gas before being introduced into the coloring vessel. Also, thecoloring process can include increasing temperature of the noble gas toor past the supercritical temperature of the noble gas before beingintroduced into the coloring vessel.

In one embodiment, the coloring process can include storing the noblegas in a supercritical fluid, gaseous, or liquid state before or afterthe coloring.

The process of coloring with the noble gases can begin with introductionof a noble gas such as argon. The argon can be compressed at roughly 500atmospheres to its supercritical form. Compression raises thetemperature; possibly to a temperature that is too high for theapplication and as such the argon may be cooled as necessary.Furthermore, the cooling can allow the argon to be stored for futurecolorings if not immediately needed. The fluid argon can be pumpedthrough a controlled temperature element that warms or cools the liquidnoble gas to the temperature at which the coloring is performed.

Coloring is accomplished in a vessel where the articles to be coloredand the colorant are introduced. The waste stream from the coloredarticles can be returned to the separation vessel. In an illustrativeexample, the supercritical argon containing dissolved colorant processbyproducts is bled off in the separator vessel, where the supercriticalargon is decompressed to return it to the gaseous state. The byproductsremain in liquid or solid form and are removed from the separator, whilethe argon gas is sent through a refrigeration or compression unit toreturn it to a liquid form for storage to be reused again. Recycling ofargon in this closed loop system means only a small portion of thecoloring solution has to be replaced over time due to system leakage.The now colored article of manufacture (e.g., parts or clothes) can beremoved from the chamber and are immediately ready for the next step inthe manufacturing process or to be worn, since no drying or rinsing isrequired to remove residual coloring solution.

FIG. 5 illustrates a representative chemical reaction between a naturalfiber and an isoquinoline derived dye. Similar chemical reaction betweendyes and articles of manufacture can produce articles that are colorfast and resistant to color degradation or lightening.

The carbon atom in carbon dioxide molecule carries a strong positivecharge even though the symmetric linear structure of carbon dioxidecreates a non-polar molecule. The positive charge on the carbon renderscarbon dioxide susceptible to nucleophilic attack. For example, carbondioxide readily reacts with amines to form carbamic acid and carbamides.The chemical reactivity of carbon dioxide imposes limitation as to whatfibers and dyes are compatible with carbon dioxide based dyeing process.

FIG. 6 illustrates representative chemical reactions between carbondioxide and several example dyes. These reactions show thatsupercritical carbon dioxide may be unfavorable for these coloringapplications because carbon dioxide may derivatize the dyes into dyederivatives, which may be unable to react with and therefore dye thearticle of manufacture. In addition, carbon dioxide is known to reactwith polymers such as triacetate and natural fibers such as cellulose,which makes it unsuitable for many coloring applications. The noblegases are chemically inert and would be a passive solvent for thereactions to take place between textile and dye. Therefore, thelimitations with carbon dioxide may not be applicable to the noblegases.

An example of a coloring process as described herein is provided asfollows. A 4-L stainless steel autoclave can be used as the coloringvessel, which is essentially a pressure autoclave. The temperature ofthe dyeing process is accomplished by setting the temperature of an oilheater. The jacket of the coloring vessel is preheated prior to eachcoloring process. After the preheating step, dye powder (0.2±0.01 g) isplaced at the bottom of the vessel, between two stainless steel filterplates with a pore size of 10 μm (e.g., colorant holder) to prevententrainment of un-dissolved dye particles. A piece of cotton (20±0.2 g)is folded around small pieces of polyester, nylon, silk and wool (each0.2±0.02 g). The textile is placed in the dyeing vessel in such a waythat supercritical argon is forced to flow through the stainless steelfilter plates and through the layers of textile. The system is thenpressurized with an air-driven plunger pump, from Williams InstrumentCompany. The argon is pumped at a flow rate of 0.10±0.02 m³/h, with acentrifugal pump with magnetic coupling from Autoclave Engineers. Theflow direction of supercritical argon through the vessel is such toprevent un-dissolved dye being exposed to the textile; first, argonflows through the dye to dissolve it, through the filter, and thenthrough the textiles. Temperature and pressure are increased slowly inthe first period of time (10 minutes to an hour) but are constantafterwards (±1° C. and ±2 bar). The coloring process is run until thedye is consumed and is on the fabric. Reaction conditions vary for dyeand textile combinations; however, a process with a vinyl sulfone dye asshown in FIG. 4 would typically be run at 113° C. and roughly 450atmospheres.

In one embodiment, the coloring process can include preparing a noblegas composition. Noble gases can be separated from the atmosphere andprocessed into pure or substantially pure noble gases. For example, thenoble gas can be prepared by liquefaction of the atmosphere, followed bydistillation, and isolation of the noble gases from other components ofthe atmosphere. The noble gas argon constitutes nearly 1% of the earth'satmosphere, and is plentiful and inexpensive. The other noble gases andmixtures of the noble gases such as krypton and xenon are also useful inthe coloring process.

In one embodiment, the coloring process can include preparing a coloringcomposition that includes a noble gas, a colorant, and an additionalsubstance. For example, noble gases can be mixed with the colorant andwith one or more additional substances, such as other gases, such ascarbon dioxide or nitrogen, or solvents such as water, or alcohols, aswell as any additional substances described herein. The compositions arethen compressed to their supercritical points where they are useful forentraining coloring agents therein (see FIG. 1). Supercritical fluidsare by definition at a temperature and pressure greater than or equal tothe supercritical temperature and pressure of the fluid.

In one embodiment, mixed component supercritical systems containing thenoble gases can be prepared. For example, a mixture can include argon,carbon dioxide, and isopropanol. By using mixed supercritical fluids,the coloring solutions can be tailored for the specific substrates beingcolored and the specific colorants being used for coloring.

Furthermore, the use of mixed systems allows for the tailoring of thepressures and temperatures required to achieve supercritical fluids.Supercritical fluids can be made with carbon dioxide and argon, argonand water, argon-acetone, or others. Table 1 shows the supercriticalpoints of various substances that can be combined with the noble gases.

TABLE 1 Supercritical properties of various solvents Super- Super-Super- Molecular critical critical critical weight temperature pressuredensity Solvent g/mol K MPa (atm) g/cm³ Carbon dioxide 44.01 304.1 7.38(72.8) 0.469 (CO₂) Water (H₂O) 18.015 647.096  22.064 (217.755) 0.322Methane (CH₄) 16.04 190.4 4.60 (45.4) 0.162 Ethane (C₂H₆) 30.07 305.34.87 (48.1) 0.203 Propane (C₃H₈) 44.09 369.8 4.25 (41.9) 0.217 Ethylene28.05 282.4 5.04 (49.7) 0.215 (C₂H₄) Propylene 42.08 364.9 4.60 (45.4)0.232 (C₃H₆) Methanol 32.04 512.6 8.09 (79.8) 0.272 (CH₃OH) Ethanol46.07 513.9 6.14 (60.6) 0.276 (C₂H₅OH) Acetone 58.08 508.1 4.70 (46.4)0.278 (C₃H₆O)

In one embodiment, the coloring composition is free of volatile organiccompounds so as to be zero-VOC.

There are many advantages to the use of supercritical noble gases, suchas, for example: being non toxic, non-carcinogenic, non-mutagenic,non-reactive, and non-combustive; do not harm the ozone layer; do notact as green house gases; being equal to or better than supercriticalcarbon dioxide in coloring ability; compression technology easilyreaches the supercritical points of argon, krypton, and xenon; and wasteremoved from the articles being colored is easily separated from thenoble gases. Also, the coloring process can be done without water sothat environmental water is not polluted by the coloring process.

In an illustrative embodiment, any of the systems, operations,processes, etc. described herein can be implemented as computer-readableinstructions stored on a computer-readable medium. For example, acomputer-readable medium can include computer-executable instructionsfor performing the coloring process, operating any of the coloringsystem components, obtaining data from any of the coloring systemcomponents, or communicating data to a remote location via a network.The computer-readable instructions can be executed by a processor of amobile unit, a network element, and/or any other computing device.

There is little distinction left between hardware and softwareimplementations of aspects of systems; the use of hardware or softwareis generally (but not always, in that in certain contexts the choicebetween hardware and software can become significant) a design choicerepresenting cost vs. efficiency tradeoffs. There are various vehiclesby which processes and/or systems and/or other technologies describedherein can be effected (e.g., hardware, software, and/or firmware), andthat the preferred vehicle will vary with the context in which theprocesses and/or systems and/or other technologies are deployed. Forexample, if an implementer determines that speed and accuracy areparamount, the implementer may opt for a mainly hardware and/or firmwarevehicle; if flexibility is paramount, the implementer may opt for amainly software implementation; or, yet again alternatively, theimplementer may opt for some combination of hardware, software, and/orfirmware.

The foregoing detailed description has set forth various embodiments ofthe devices and/or processes via the use of block diagrams, flowcharts,and/or examples. Insofar as such block diagrams, flowcharts, and/orexamples contain one or more functions and/or operations, it will beunderstood by those within the art that each function and/or operationwithin such block diagrams, flowcharts, or examples can be implemented,individually and/or collectively, by a wide range of hardware, software,firmware, or virtually any combination thereof. In one embodiment,several portions of the subject matter described herein may beimplemented via Application Specific Integrated Circuits (ASICs), FieldProgrammable Gate Arrays (FPGAs), digital signal processors (DSPs), orother integrated formats. However, those skilled in the art willrecognize that some aspects of the embodiments disclosed herein, inwhole or in part, can be equivalently implemented in integratedcircuits, as one or more computer programs running on one or morecomputers (e.g., as one or more programs running on one or more computersystems), as one or more programs running on one or more processors(e.g., as one or more programs running on one or more microprocessors),as firmware, or as virtually any combination thereof, and that designingthe circuitry and/or writing the code for the software and or firmwarewould be well within the skill of one of skill in the art in light ofthis disclosure. In addition, those skilled in the art will appreciatethat the mechanisms of the subject matter described herein are capableof being distributed as a program product in a variety of forms, andthat an illustrative embodiment of the subject matter described hereinapplies regardless of the particular type of signal bearing medium usedto actually carry out the distribution. Examples of a signal bearingmedium include, but are not limited to, the following: a recordable typemedium such as a floppy disk, a hard disk drive, a CD, a DVD, a digitaltape, a computer memory, etc.; and a transmission type medium such as adigital and/or an analog communication medium (e.g., a fiber opticcable, a waveguide, a wired communications link, a wirelesscommunication link, etc.).

Those skilled in the art will recognize that it is common within the artto describe devices and/or processes in the fashion set forth herein,and thereafter use engineering practices to integrate such describeddevices and/or processes into data processing systems. That is, at leasta portion of the devices and/or processes described herein can beintegrated into a data processing system via a reasonable amount ofexperimentation. Those having skill in the art will recognize that atypical data processing system generally includes one or more of asystem unit housing, a video display device, a memory such as volatileand non-volatile memory, processors such as microprocessors and digitalsignal processors, computational entities such as operating systems,drivers, graphical user interfaces, and applications programs, one ormore interaction devices, such as a touch pad or screen, and/or controlsystems including feedback loops and control motors (e.g., feedback forsensing position and/or velocity; control motors for moving and/oradjusting components and/or quantities). A typical data processingsystem may be implemented utilizing any suitable commercially availablecomponents, such as those typically found in datacomputing/communication and/or network computing/communication systems.

The herein described subject matter sometimes illustrates differentcomponents contained within, or connected with, different othercomponents. It is to be understood that such depicted architectures aremerely exemplary, and that in fact many other architectures can beimplemented which achieve the same functionality. In a conceptual sense,any arrangement of components to achieve the same functionality iseffectively “associated” such that the desired functionality isachieved. Hence, any two components herein combined to achieve aparticular functionality can be seen as “associated with” each othersuch that the desired functionality is achieved, irrespective ofarchitectures or intermedial components. Likewise, any two components soassociated can also be viewed as being “operably connected”, or“operably coupled”, to each other to achieve the desired functionality,and any two components capable of being so associated can also be viewedas being “operably couplable”, to each other to achieve the desiredfunctionality. Specific examples of operably couplable include but arenot limited to physically mateable and/or physically interactingcomponents and/or wirelessly interactable and/or wirelessly interactingcomponents and/or logically interacting and/or logically interactablecomponents.

With respect to the use of substantially any plural and/or singularterms herein, those having skill in the art can translate from theplural to the singular and/or from the singular to the plural as isappropriate to the context and/or application. The varioussingular/plural permutations may be expressly set forth herein for sakeof clarity.

It will be understood by those within the art that, in general, termsused herein, and especially in the appended claims (e.g., bodies of theappended claims) are generally intended as “open” terms (e.g., the term“including” should be interpreted as “including but not limited to,” theterm “having” should be interpreted as “having at least,” the term“includes” should be interpreted as “includes but is not limited to,”etc.). It will be further understood by those within the art that if aspecific number of an introduced claim recitation is intended, such anintent will be explicitly recited in the claim, and in the absence ofsuch recitation no such intent is present. For example, as an aid tounderstanding, the following appended claims may contain usage of theintroductory phrases “at least one” and “one or more” to introduce claimrecitations. However, the use of such phrases should not be construed toimply that the introduction of a claim recitation by the indefinitearticles “a” or “an” limits any particular claim containing suchintroduced claim recitation to embodiments containing only one suchrecitation, even when the same claim includes the introductory phrases“one or more” or “at least one” and indefinite articles such as “a” or“an” (e.g., “a” and/or “an” should be interpreted to mean “at least one”or “one or more”); the same holds true for the use of definite articlesused to introduce claim recitations. In addition, even if a specificnumber of an introduced claim recitation is explicitly recited, thoseskilled in the art will recognize that such recitation should beinterpreted to mean at least the recited number (e.g., the barerecitation of “two recitations,” without other modifiers, means at leasttwo recitations, or two or more recitations). Furthermore, in thoseinstances where a convention analogous to “at least one of A, B, and C,etc.” is used, in general such a construction is intended in the senseone having skill in the art would understand the convention (e.g., “asystem having at least one of A, B, and C” would include but not belimited to systems that have A alone, B alone, C alone, A and Btogether, A and C together, B and C together, and/or A, B, and Ctogether, etc.). In those instances where a convention analogous to “atleast one of A, B, or C, etc.” is used, in general such a constructionis intended in the sense one having skill in the art would understandthe convention (e.g., “a system having at least one of A, B, or C” wouldinclude but not be limited to systems that have A alone, B alone, Calone, A and B together, A and C together, B and C together, and/or A,B, and C together, etc.). It will be further understood by those withinthe art that virtually any disjunctive word and/or phrase presenting twoor more alternative terms, whether in the description, claims, ordrawings, should be understood to contemplate the possibilities ofincluding one of the terms, either of the terms, or both terms. Forexample, the phrase “A or B” will be understood to include thepossibilities of “A” or, “B” or “A and B.”

In addition, where features or aspects of the disclosure are describedin terms of Markush groups, those skilled in the art will recognize thatthe disclosure is also thereby described in terms of any individualmember or subgroup of members of the Markush group.

As will be understood by one skilled in the art, for any and allpurposes, such as in terms of providing a written description, allranges disclosed herein also encompass any and all possible subrangesand combinations of subranges thereof. Any listed range can be easilyrecognized as sufficiently describing and enabling the same range beingbroken down into at least equal halves, thirds, quarters, fifths,tenths, etc. As a non-limiting example, each range discussed herein canbe readily broken down into a lower third, middle third and upper third,etc. As will also be understood by one skilled in the art all languagesuch as “up to,” “at least,” and the like include the number recited andrefer to ranges which can be subsequently broken down into subranges asdiscussed above. Finally, as will be understood by one skilled in theart, a range includes each individual member. Thus, for example, a grouphaving 1-3 cells refers to groups having 1, 2, or 3 cells. Similarly, agroup having 1-5 cells refers to groups having 1, 2, 3, 4, or 5 cells,and so forth.

From the foregoing, it will be appreciated that various embodiments ofthe present disclosure have been described herein for purposes ofillustration, and that various modifications may be made withoutdeparting from the scope and spirit of the present disclosure.Accordingly, the various embodiments disclosed herein are not intendedto be limiting, with the true scope and spirit being indicated by thefollowing claims.

All embodiments of the coloring system, coloring compositions, orcoloring processes can be used in an interchangeable manner and allembodiments can be used together, as allowable.

1. A composition comprising: a colorant; a supercritical fluidconsisting essentially of a noble gas having the colorant dissolved,suspended, or absorbed in the supercritical fluid; and an article ofmanufacture located in the supercritical fluid.
 2. (canceled)
 3. Thecomposition of claim 1, wherein the colorant is one of the following: adye; an organic dye; an inorganic dye; a pigment; or a stain. 4.-13.(canceled)
 14. The composition of claim 1, wherein the composition isdevoid of a volatile organic compound.
 15. The composition of claim 1,wherein the colorant is present in a sufficient amount to color anarticle of manufacture which is in contact with the noble gas in thesupercritical fluid state.
 16. The composition of claim 1, wherein thearticle of manufacture includes a textile, polymer, plastic, wood,ceramic, glass, metal or alloy, or combination thereof.
 17. A coloringsystem comprising: a noble gas; a colorant that is miscible in the noblegas when in a supercritical state; one or more vessels configured to:convert the noble gas into a supercritical fluid; and receive and coloran article of manufacture with the noble gas in the supercritical fluidstate having the colorant dissolved, suspended, or absorbed in thesupercritical noble gas; and a separator vessel fluidly coupled to theone or more vessels and configured to decompress the supercritical noblegas to separate the noble gas from the colorant and/or colorantbyproduct, wherein the separator vessel includes a gas outlet and asolids/liquids outlet. 18.-26. (canceled)
 27. The coloring system ofclaim 17, further comprising a noble gas storage vessel configured tostore the noble gas in a supercritical fluid, gaseous, or liquid state.28. The coloring system of claim 17, further comprising a cooling unitconfigured to receive the noble gas in a supercritical fluid state orgaseous state and to reduce the temperature of the noble gas to a liquidstate for storage in a noble gas storage vessel. 29.-31. (canceled) 32.The coloring system of claim 17, further comprising an additionalsubstance dissolved, suspended, or absorbed in the supercritical noblegas selected from a different noble gas, carbon dioxide, air, oxygen,nitrogen, water, alcohols, aldehydes, amines, hydrocarbons, aromatichydrocarbons, phenols, bleaches, or combinations thereof.
 33. Thecoloring system of claim 32, wherein the additional substance is asfollows: the alcohol is selected from a group consisting of methanol,ethanol, butanol, propanol, and hexanol; the ketone is selected from agroup consisting of acetone, acetyl ketone, and hexanone; the aldehydeis selected from a group consisting of formaldehyde and acetyldehyde;the hydrocarbon is selected from a group consisting of methane, ethane,propane, butane, ethylene, and propylene; or the halogenated hydrocarbonis selected from a group consisting of iodoethane, methylene chloride,and chloroform. 34.-40. (canceled)
 41. A coloring process comprising:converting a noble gas into a supercritical fluid state; combining acolorant with the noble gas in the supercritical fluid state within acoloring vessel; coloring an article of manufacture with the noble gasin the supercritical fluid state having the colorant dissolved,suspended, or absorbed in the supercritical noble gas; decompressing thesupercritical noble gas to a gaseous state; and separating the noble gasfrom the colorant and/or colorant byproducts in a separator vessel. 42.The coloring process of claim 41, further comprising combining anadditional substance with the noble gas, wherein the additionalsubstance is selected from a different noble gas, carbon dioxide, air,oxygen, nitrogen, water, alcohols, aldehydes, amines, hydrocarbons,aromatic hydrocarbons, phenols, bleaches, or combinations thereof. 43.(canceled)
 44. The coloring process of claim 42, wherein the additionalsubstance is as follows: the alcohol is selected from a group consistingof methanol, ethanol, butanol, propanol, and hexanol; the ketone isselected from a group consisting of acetone, acetyl ketone, andhexanone; the aldehyde is selected from a group consisting offormaldehyde and acetyldehyde; the hydrocarbon is selected from a groupconsisting of methane, ethane, propane, butane, ethylene, and propylene;or the halogenated hydrocarbon is selected from a group consisting ofiodoethane, methylene chloride, and chloroform. 45.-54. (canceled) 55.The coloring process of claim 41, wherein the coloring comprisesgenerating bubbles in the presence of the article of manufacture. 56.The coloring process of claim 41, wherein the coloring comprisesagitating the article of manufacture.
 57. The coloring process of claim56, wherein the agitating is from mechanical agitation.
 58. The coloringprocess of claim 56, wherein the agitating is from bubble generation.59.-61. (canceled)
 62. The coloring process of claim 41, furthercomprising cooling the noble gas from a gaseous state to a liquid stateafter being separated from the colorant or colorant byproducts. 63.-65.(canceled)
 66. The coloring process of claim 41, further comprisingintroducing the noble gas in the supercritical fluid state into acoloring vessel where the colorant and article of manufacture have beenpreviously introduced. 67.-69. (canceled)
 70. The coloring process ofclaim 41, further comprising storing the noble gas in a supercriticalfluid, gaseous, or liquid state after being separated from the colorantand/or colorant byproducts. 71.-79. (canceled)